Selective Construction and Structural Transformation of Homogeneous Linear Metallacatenane and Metallacatenane Assemblies

• Published in: Angewandte Chemie 2024-04, Vol.136 (18)
• Main Authors: Wei‐Long Shan, Huan‐Huan Hou, Si, Nian, Cai‐Xia Wang, Yuan, Guozan, Gao, Xiang, Guo‐Xin Jin
• Format: Article
• Language: English
• Subjects: Bonding strength; Chemical synthesis; Hydrogen bonding; Hydrogen bonds; Magnetic resonance spectroscopy; Mass spectrometry; Mass spectroscopy; Molecular structure; NMR spectroscopy; Precursors; Rhodium; Self-assembly; X-ray diffraction
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.202402198

Although the synthesis of mechanically interlocked molecules has been extensively researched, selectively constructing homogeneous linear [4]catenanes remains a formidable challenge. Here, we selectively constructed a homogeneous linear metalla[4]catenane in a one‐step process through the coordination‐driven self‐assembly of a bidentate benzothiadiazole derivative ligand and a binuclear half‐sandwich rhodium precursor. The formation of metalla[4]catenanes was facilitated by cooperative interactions between strong sandwich‐type π‐π stacking and non‐classical hydrogen bonds between the components. Moreover, by modulating the aromatic substituents on the binuclear precursor, two homogeneous metalla[2]catenanes were obtained. The molecular structures of these metallacatenanes were unambiguously characterized by single‐crystal X‐ray diffraction analysis. Additionally, reversible structural transformation between metal‐catenanes and the corresponding metallarectangles could be achieved by altering their concentration, as confirmed by mass spectrometry and NMR spectroscopy studies.